Fluorinated alkoxyvinyl ethers and methods for preparing fluorinated alkoxyvinyl ethers

ABSTRACT

An alkoxyvinyl ether is disclosed having the chemical structure R f C(OR)═CHR f ′, wherein R f  is an at least partially fluorinated functional group having at least one carbon atom, R f ′ is an at least partially fluorinated functional group having at least two carbon atoms, and R is a functional group. A method for preparing an alkoxyvinyl ether is disclosed, comprising R f CFHCFHR f ′+KOH/ROH→R f C(OR)═CHR f ′, wherein R f  is a perfluoro functional group, R f ′ is a perfluoro functional group, and R is an alkyl functional group. Another method for preparing an alkoxyvinyl ether is disclosed, comprising R f CF═CHR f ′+KOH/ROH→R f C(OR)═CHR f ′, wherein R f  is a perfluoro functional group, R f ′ is a perfluoro functional group, and R is an alkyl functional group.

This application claims the benefit of Application No. 62/745,733, filedon Oct. 15, 2018. The disclosure of Application No. 62/745,733 is herebyincorporated by reference.

FIELD OF THE INVENTION

The present invention is directed to alkoxyvinyl ethers and methods forpreparing alkoxyvinyl ethers. More particularly, the present inventionis directed to fluorinated alkoxyvinyl ethers and methods for preparingfluorinated alkoxyvinyl ethers.

BACKGROUND OF THE INVENTION

Certain fluorinated materials of general structure R_(f)C(OCH₃)═CFR_(f)′are known, and such materials may be prepared by the reaction ofalcohols with a variety of perfluorinated olefins, such as F-pentene-2(known as a commercial intermediate) or F-heptenes (known as wastestream components form the production of other materials). By way ofexample, the product of the reaction of F-heptenes with methanol(HFX-110) has been proposed for use as a solvent with low toxicity andlow global warming potential.

However, to date there has been no disclosure in the scientificliterature of fluorinated chemical species having the general structureof R_(f)C(OR)═CHR_(f)′, wherein R_(f)′ has at least two carbon atoms.Nor has there been any disclosure to date of a basic alcohol reactionpathway to prepare fluorinated chemical species having the generalstructure of R_(f)C(OR)═CHR_(f)′, wherein R is an alkyl functionalgroup.

BRIEF DESCRIPTION OF THE INVENTION

In an exemplary embodiment, an alkoxyvinyl ether has the chemicalstructure R_(f)C(OR)═CHR_(f)′, wherein R_(f) is an at least partiallyfluorinated functional group having at least one carbon atom, R_(f)′ isan at least partially fluorinated functional group having at least twocarbon atoms, and R is a functional group.

In another exemplary embodiment, a method for preparing an alkoxyvinylether includes R_(f)CFHCFHR_(f)′+KOH/ROH→R_(f)C(OR)═CHR_(f)′, whereinR_(f) is a perfluoro functional group, R_(f)′ is a perfluoro functionalgroup, and R is an alkyl functional group.

In another exemplary embodiment, a method for preparing an alkoxyvinylether includes R_(f)CF═CHR_(f)′+KOH/ROH→R_(f)C(OR)═CHR_(f)′, whereinR_(f) is a perfluoro functional group, R_(f)′ is a perfluoro functionalgroup, and R is an alkyl functional group.

Another embodiment of the invention relates to any combination of theforegoing alkoxyvinyl ethers wherein:

-   -   R_(f) is a perfluoro functional group having at least one carbon        atom;    -   R_(f)′ is a perfluoro functional group having at least two        carbon atoms; and    -   R is a functional group having at least one carbon atom.

Another embodiment of the invention relates to any combination of theforegoing alkoxyvinyl ethers, wherein:

-   -   R_(f) is a perfluoroalkyl functional group;    -   R_(f)′ is a perfluoroalkyl functional group having at least two        carbon atoms; and    -   R is an alkyl functional group.

Another embodiment of the invention relates to any combination of theforegoing alkoxyvinyl ethers, wherein:

-   -   R_(f) is a C₁₋₁₂ perfluoroalkyl functional group;    -   R_(f)′ is a C₂₋₁₂ perfluoroalkyl functional group; and    -   R is a C₁₋₁₂ alkyl functional group.

Another embodiment of the invention relates to any combination of theforegoing alkoxyvinyl ethers, wherein:

-   -   R_(f) is selected from the group consisting of CF₃, C₂F₅,        n-C₃F₇, iso-C₃F₇, n-C₄F₉, sec-C₄F₉, iso-C₄F₉, and tert-C₄F₉;    -   R_(f)′ is selected from the group consisting of C₂F₅, n-C₃F₇,        iso-C₃F₇, n-C₄F₉, sec-C₄F₉, iso-C₄F₉, and tert-C₄F₉; and    -   R is selected from the group consisting of CH₃, C₂H₅, n-C₃H₇,        iso-C₃H₇, n-C₄H₉, sec-C₄H₉, iso-C₄H₉, and tert-C₄H₉.

Another embodiment of the invention relates to any combination of theforegoing alkoxyvinyl ethers, wherein:

-   -   R_(f) is a partially fluorinated functional group having at        least one carbon atom;    -   R_(f)′ is a partially fluorinated functional group having at        least two carbon atoms;    -   and    -   R is a functional group having at least one carbon atom.

Another embodiment of the invention relates to any combination of theforegoing alkoxyvinyl ethers, wherein:

-   -   R_(f) is a perfluoro functional group having at least one carbon        atom;    -   R_(f)′ is a partially fluorinated functional group having at        least two carbon atoms; and    -   R is a functional group having at least one carbon atom.

Another embodiment of the invention relates to any combination of theforegoing alkoxyvinyl ethers, wherein:

-   -   R_(f) is a partially fluorinated functional group having at        least one carbon atom;    -   R_(f)′ is a perfluoro functional group having at least two        carbon atoms; and    -   R is a functional group having at least one carbon atom.

Another embodiment of the invention relates to any combination of theforegoing embodiments, wherein:

-   -   R_(f) is selected from the group consisting of CF₃, CF₂H, C₂F₅,        C₂F₄H, n-C₃F₇, n-C₃F₆H, iso-C₃F₇, iso-C₃F₆H, n-C₄F₉, n-C₄F₈H,        sec-C₄F₉, sec-C₄F₈H, iso-C₄F₉, iso-C₄F₈H, and tert-C₄F₉,        tert-C₄F₈H;    -   R_(f)′ is selected from the group consisting of C₂F₅, C₂F₄H,        n-C₃F₇, n-C₃F₆H, iso-C₃F₇, iso-C₃F₆H, n-C₄F₉, n-C₄F₈H, sec-C₄F₉,        sec-C₄F₈H, iso-C₄F₉, iso-C₄F₈H, and tert-C₄F₉, tert-C₄F₈H; and    -   R is selected from the group consisting of CH₃, C₂H₅, n-C₃H₇,        iso-C₃H₇, n-C₄H₉, sec-C₄H₉, iso-C₄H₉, and tert-C₄H₉.

Another embodiment of the invention relates to any combination of theforegoing embodiments wherein R_(f) and R_(f)′ are the same.

Another embodiment of the invention relates to any combination of theforegoing embodiments, wherein R_(f) and R_(f)′ are distinct.

Another embodiment of the invention relates to any combination of theforegoing embodiments, wherein the alkoxyvinyl ether is an E-isomer.

Another embodiment of the invention relates to any combination of theforegoing embodiments, wherein the alkoxyvinyl ether is a Z-isomer.

Another embodiment of the invention relates to any combination of theforegoing embodiments wherein the alkoxyvinyl ether is a mixture of E-and Z-isomers.

Another embodiment of the invention relates to any combination of theforegoing embodiments, wherein the chemical structure isCF₃C(OCH₃)═CHC₂F₅.

Another embodiment of the invention relates to any combination of theforegoing embodiments, wherein the chemical structure isCF₃C(OC₂H₅)═CHC₂F₅.

Another embodiment of the invention relates to any combination of theforegoing embodiments, wherein the chemical structure isCF₃C(OC₃H₇)═CHC₂F₅.

Another embodiment of the invention relates to any combination of theforegoing embodiments, wherein the chemical structure isC₂F₅C(OCH₃)═CHC₃F₇.

One embodiment of the invention relates to a method for preparing analkoxyvinyl ether, comprising:R_(f)CFHCFHR_(f)′+Base/ROH→R_(f)C(OR)═CHR_(f)′

-   -   wherein:        -   R_(f) is a perfluoro functional group;        -   R_(f)′ is a perfluoro functional group; and        -   R is an alkyl functional group.

Another embodiment of the invention relates to a method for preparing analkoxyvinyl ether, comprising:R_(f)CF═CHR_(f)′+Base/ROH→R_(f)C(OR)═CHR_(f)′

-   -   wherein:        -   R_(f) is a perfluoro functional group;        -   R_(f)′ is a perfluoro functional group; and        -   R is an alkyl functional group.

One embodiment of the invention relates to a solvent comprising anycombination of the foregoing alkoxyvinyl ethers and at least one memberselected from the group consisting of alcohols, ethers, tetrahydrofuran(THF), amides, or aromatic solvents.

Another embodiment of the invention relates to an alkoxyvinylcomposition comprising:

-   -   any combination of the foregoing alkoxyvinyl ethers;    -   at least one solvent including at least one of alcohols, ethers,        tetrahydrofuran (THF), amides, or aromatic solvents; and    -   at least one base including at least one of KOH, NaOH, LiOH,        Ca(OH)₂, tertiary amines, or alkoxides of alkali metals ROM        (M=Li, Na, K, Cs).

Another embodiment of the invention relates to a process fortransferring heat, comprising:

-   -   providing an article;    -   contacting the article with a heat transfer media;    -   wherein the heat transfer media comprises any combination of the        foregoing alkoxyvinyl ethers.

Another embodiment of the invention relates to the foregoing processes,wherein the boiling point of the alkoxyvinyl ether is between about 72degrees Celsius and about 81 degrees Celsius.

Another embodiment of the invention relates to a process for treating asurface, comprising:

-   -   providing a surface;    -   contacting the surface with a treatment composition;    -   wherein the surface includes a treatable material deposited        thereon; and    -   wherein the treatment composition comprises any of the foregoing        combinations of alkoxyvinyl ethers.

Another embodiment of the invention relates to the foregoing processes,wherein the treatment composition substantially dissolves the treatablematerial.

Another embodiment of the invention relates to a process for forming acomposition comprising:

-   -   providing a solute;    -   contacting the solute with a solvent;    -   wherein the solvent comprises any combination of the foregoing        alkoxyvinyl ethers.

Another embodiment of the invention relates to a process for providingelectrical insulation, comprising:

-   -   providing a first charged surface;    -   providing a second charged surface;    -   contacting the first charged surface and the second charged        surface with a dielectric composition;    -   wherein the dielectric composition comprises any combination of        the foregoing alkoxyvinyl ethers.

Another embodiment of the invention relates to the foregoing processes,wherein the dielectric composition forms a continuous pathway betweenthe first charged surface and the second charged surface.

The various embodiments of the invention can be used alone or incombinations with each other. Other features and advantages of thepresent invention will be apparent from the following more detaileddescription of the preferred embodiment, taken in conjunction with theaccompanying drawings, which illustrate, by way of example, theprinciples of the invention.

DETAILED DESCRIPTION OF THE INVENTION

Provided are exemplary fluorinated alkoxyvinyl ethers and methods forpreparing fluorinated alkoxyvinyl ethers. Embodiments of the presentdisclosure, in comparison to compositions of matter and methods notutilizing one or more features disclosed herein, include advantageoussolvating properties, advantageous boiling point ranges, advantageousdegreasing properties, advantageous heat transfer properties, decreasedflammability, decreased atmospheric life time, increased polarity, orcombinations thereof.

In some embodiments, the alkoxyvinyl ethers may find useful applicationas a cleaning agent or degreasing agent, a heat transfer media, asolvent, and/or a dielectric.

In one embodiment, an alkoxyvinyl ether has the following chemicalstructure:R_(f)C(OR)═CHR_(f)′

R_(f) may be a partially fluorinated functional group or a perfluorofunctional group, including, but not limited to, a partially fluorinatedfunctional group having at least one carbon atom, a perfluoro functionalgroup having at least one carbon atom, a partially fluorinated alkylgroup, a perfluoroalkyl group, a C₁₋₁₂ partially fluorinated alkylfunctional group, a C₁₋₁₂ perfluoroalkyl functional group, CF₃, CF₂H,C₂F₅, C₂F₄H, n-C₃F₇, n-C₃F₆H, iso-C₃F₇, iso-C₃F₆H, n-C₄F₉, n-C₄F₈H,sec-C₄F₉, sec-C₄F₈H, iso-C₄F₉, iso-C₄F₈H, tert-C₄F₉, or tert-C₄F₈H.

R_(f)′ may be a partially fluorinated functional group or a perfluorofunctional group, including, but not limited to, a partially fluorinatedfunctional group having at least two carbon atoms, a perfluorofunctional group having at least two carbon atoms, a partiallyfluorinated alkyl group having at least two carbon atoms, aperfluoroalkyl group having at least two carbon atoms, a C₂₋₁₂ partiallyfluorinated alkyl functional group, a C₂₋₁₂ perfluoroalkyl functionalgroup, C₂F₅, C₂F₄H, n-C₃F₇, n-C₃F₆H, iso-C₃F₇, iso-C₃F₆H, n-C₄F₉,n-C₄F₈H, sec-C₄F₉, sec-C₄F₈H, iso-C₄F₉, iso-C₄F₈H, tert-C₄F₉, ortert-C₄F₈H.

R is a functional group which may be, but is not limited to, afunctional group having at least one carbon atom, an alkyl functionalgroup, a C₁₋₁₂ alkyl functional group, CH₃, C₂H₅, n-C₃H₇, iso-C₃H₇,n-C₄H₉, sec-C₄H₉, iso-C₄H₉, or tert-C₄H₉.

The alkoxyvinyl ether may include any suitable combination of specificspecies of R, R_(f), and R_(f)′ disclosed herein. R_(f) and R_(f)′ maybe identical or distinct from one another.

In one embodiment, R_(f) is an at least partially fluorinated functionalgroup having at least one carbon atom, R_(f)′ is an at least partiallyfluorinated functional group having at least two carbon atoms, and R isa functional group.

In another embodiment, R_(f) is a perfluoro functional group having atleast one carbon atom, R_(f)′ is a perfluoro functional group having atleast two carbon atoms, and R is a functional group having at least onecarbon atom.

In yet another embodiment, R_(f) is a perfluoroalkyl functional grouphaving at least one carbon atom, R_(f)′ is a perfluoroalkyl functionalgroup having at least two carbon atoms, and R is an alkyl functionalgroup.

In still another embodiment, R_(f) is a C₁₋₁₂ perfluoroalkyl functionalgroup, R_(f)′ is a C₂₋₁₂ perfluoroalkyl functional group, and R is aC₁₋₁₂ alkyl functional group.

In another embodiment, R_(f) is selected from the group consisting ofCF₃, C₂F₅, n-C₃F₇, iso-C₃F₇, n-C₄F₉, sec-C₄F₉, iso-C₄F₉, and tert-C₄F₉,R_(f)′ is selected from the group consisting of C₂F₅, n-C₃F₇, iso-C₃F₇,n-C₄F₉, sec-C₄F₉, iso-C₄F₉, and tert-C₄F₉, and R is selected from thegroup consisting of CH₃, C₂H₅, n-C₃H₇, iso-C₃H₇, n-C₄H₉, sec-C₄H₉,iso-C₄H₉, and tert-C₄H₉.

In yet another embodiment, R_(f) is a partially fluorinated functionalgroup having at least one carbon atom, R_(f)′ is a partially fluorinatedfunctional group having at least two carbon atoms, and R is a functionalgroup having at least one carbon atom.

In still another embodiment, R_(f) is a perfluoro functional grouphaving at least one carbon atom, R_(f)′ is a partially fluorinatedfunctional group having at least two carbon atoms, and R is a functionalgroup having at least one carbon atom.

In another embodiment, R_(f) is a partially fluorinated functional grouphaving at least one carbon atom, R_(f)′ is a perfluoro functional grouphaving at least two carbon atoms, and R is a functional group having atleast one carbon atom.

In yet another embodiment, R_(f) is selected from the group consistingof CF₃, CF₂H, C₂F₅, C₂F₄H, n-C₃F₇, n-C₃F₆H, iso-C₃F₇, iso-C₃F₆H, n-C₄F₉,n-C₄F₈H, sec-C₄F₉, sec-C₄F₈H, iso-C₄F₉, iso-C₄F₈H, and tert-C₄F₉,tert-C₄F₈H, R_(f)′ is selected from the group consisting of C₂F₅, C₂F₄H,n-C₃F₇, n-C₃F₆H, iso-C₃F₇, iso-C₃F₆H, n-C₄F₉, n-C₄F₈H, sec-C₄F₉,sec-C₄F₈H, iso-C₄F₉, iso-C₄F₈H, and tert-C₄F₉, tert-C₄F₈H, and R isselected from the group consisting of CH₃, C₂H₅, n-C₃H₇, iso-C₃H₇,n-C₄H₉, sec-C₄H₉, iso-C₄H₉, and tert-C₄H₉.

The alkoxyvinyl ether may be an E-isomer, a Z-isomer, or a mixture of E-and Z-isomers.

The alkoxyvinyl ether may have any suitable chemical structure,including, but not limited to, CF₃C(OCH₃)═CHC₂F₅, CF₃C(OC₂H₅)═CHC₂F₅,CF₃C(OC₃H₇)═CHC₂F₅, and C₂F₅C(OCH₃)═CHC₃F₇.

In one embodiment, an alkoxyvinyl ether having the structureR_(f)C(OR)═CHR_(f)′ has a reduced flammability compared to analkoxyvinyl ether having the structure R_(f)C(OR)═CFR_(f)′. By way ofexample, on the basis of calculated heats of formation,CF₃C(OCH₃)═CHC₂F₅ has a heat of combustion of about 2.08 kcal/g ascompared to a heat of combustion of 2.58 kcal/g for CF₃C(OCH₃)═CHCF₃.The inventive alkoxyvinyl ethers can have a heat of combustion of lessthan about 2.1 kcal/g and, as a result, the inventive compounds can havea low or non-flammability rating.

In one embodiment, an alkoxyvinyl ether having the structureR_(f)C(OR)═CHR_(f)′ has a reduced atmospheric lifetime compared to analkoxyvinyl ether having the structure R_(f)C(OR)═CFR_(f)′. Theinventive alkoxyvinyl ethers can have an atmospheric lifetime rangingfrom about 10 to 200 days and, typically, less than 100 days.

In one embodiment, an alkoxyvinyl ether having the structureR_(f)C(OR)═CHR_(f)′ has an increased polarity compared to an alkoxyvinylether having the structure R_(f)C(OR)═CFR_(f)′. By way of example, onthe basis of calculated dipole moments, CF₃C(OCH₃)═CHC₂F₅ has a dipolemoment of 2.5460 D as compared to a dipole moment of 2.3965 D forCF₃C(OCH₃)═CFC₂F₅. The inventive alkoxyvinyl ethers can have a dipolemoment of about 2 to about 5 D and in some cases about 2 to about 3D.

In one embodiment, a method for preparing an alkoxyvinyl ether,includes:R_(f)CFHCFHR_(f)′+Base/ROH→R_(f)C(OR)═CHR_(f)′

The method may include a prior step of:R_(f)CF═CFR_(f)′+H₂→R_(f)CFHCFHR_(f)′

In another embodiment, a method for preparing an alkoxyvinyl ether,includes:R_(f)CF═CHR_(f)′+Base/ROH→R_(f)C(OR)═CHR_(f)′

With respect to the methods for preparing the alkoxyvinyl ether: R_(f)may be a partially fluorinated functional group or a perfluorofunctional group, including, but not limited to, a partially fluorinatedfunctional group having at least one carbon atom, a perfluoro functionalgroup having at least one carbon atom, a partially fluorinated alkylgroup, a perfluoroalkyl group, a C₁₋₁₂ partially fluorinated alkylfunctional group, a C₁₋₁₂ perfluoroalkyl functional group, CF₃, CF₂H,C₂F₅, C₂F₄H, n-C₃F₇, n-C₃F₆H, iso-C₃F₇, iso-C₃F₆H, n-C₄F₉, n-C₄F₈H,sec-C₄F₉, sec-C₄F₈H, iso-C₄F₉, iso-C₄F₈H, tert-C₄F₉, or tert-C₄F₈H;R_(f)′ may be a partially fluorinated functional group or a perfluorofunctional group, including, but not limited to, a partially fluorinatedfunctional group having at least one carbon atom, a perfluoro functionalgroup having at least one carbon atom, a partially fluorinated alkylgroup, a perfluoroalkyl group, a C₁₋₁₂ partially fluorinated alkylfunctional group, a C₁₋₁₂ perfluoroalkyl functional group, CF₃, CF₂H,C₂F₅, C₂F₄H, n-C₃F₇, n-C₃F₆H, iso-C₃F₇, iso-C₃F₆H, n-C₄F₉, n-C₄F₈H,sec-C₄F₉, sec-C₄F₈H, iso-C₄F₉, iso-C₄F₈H, tert-C₄F₉, or tert-C₄F₈H; andR is a functional group which may be, but is not limited to, an alkylfunctional group, a C₁₋₁₂ alkyl functional group, CH₃, C₂H₅, n-C₃H₇,iso-C₃H₇, n-C₄H₉, sec-C₄H₉, iso-C₄H₉, or tert-C₄H₉. The method mayinclude any suitable combination of specific species of R, R_(f), andR_(f)′ disclosed herein. R_(f) and R_(f)′ may be identical or distinctfrom one another.

In one embodiment of the invention, at least one alkyoxyl vinyl ethercan interact or react with elimination of HF. In a particularembodiment, the elimination of HF can produce at least one alkyoxylvinyl ether with an additional double bond. In one particular embodimentat least one of the following groups can eliminate HF under certainreaction conditions: iso-C₃F₆H, n-C₄F₈H, sec-C₄F₈H, iso-C₄F₈H, ortert-C₄F₈H. Without wishing to be bound by any theory or explanation, itis believed that an excess amount of base can promote the HFelimination.

The base may be any suitable base, including, but not limited to, KOH,NaOH, LiOH, Ca(OH)₂, tertiary amines, and/or alkoxides of alkali metalsROM (M=Li, Na, K, Cs). The amount of base will be at least two moles permole of reactant. If desired, the amount of reactant can be in excess ofthe molar amount of base and, unreacted material (if any) can berecycled in order to increase selectivity.

In some embodiments, the reaction composition may further include anysuitable solvent, including, but not limited to, alcohols, ethers (e.g.,glymes, diethyl ether, methyl-t-butyl ether), tetrahydrofuran (THF),amides, and/or aromatic solvents (e.g., benzene, toluene, xylenes). Theamount of solvent can range from about 0.5 to about 500 moles per moleof reactant and, in some cases, about 5 to about 100 moles of solvent.

In some embodiments, the reaction may be performed in the absence ofsolvent, under phase-transfer catalysis (PTC) conditions. Suitable phasetransfer catalysts include, but are not limited to, tetraalkylammoniumsalts, phosphonium salts, and/or crown ethers. The amount of catalystcan range from about 0.1 to about 50 mole percent relative to thereactant and, in some cases, about 5 to 15 mole percent.

In some embodiments, the reaction may be performed at a temperature ofat least −20 degrees Celsius, at least 0 degrees Celsius, at least 10degrees Celsius, at least 20 degrees Celsius, at least 25 degreesCelsius, at least 30 degrees Celsius, at least 40 degrees Celsius, lessthan 110 degrees Celsius, less than 100 degrees Celsius, less than 90degrees Celsius, less than 80 degrees Celsius, less than 70 degreesCelsius, less than 60 degrees Celsius, less than 50 degrees Celsius, andcombinations thereof. The reaction pressure can be conducted atatmospheric pressure and, if desired, the pressure can be increased togreater than atmospheric pressure (e.g., about 1 to about 100atmospheres).

The alkoxyvinyl ether may be useful in various applications. In anembodiment, the alkoxyvinyl ether may be used in accordance withconvention equipment and methods to transfer heat. The process mayinclude providing an article and contacting the article with a heattransfer media including the alkoxyvinyl ether. In some embodiments, thearticle may include electrical equipment (e.g., circuit board, computer,display, semiconductor chip, or transformer), a heat transfer surface(e.g., heat sink), or article of clothing (e.g., a body suit).

In another embodiment, the alkoxyvinyl ether may be used in a processfor treating a surface. The process may include providing a surfacehaving a treatable material deposited thereon and contacting the surfacewith a treatment composition including the alkoxyvinyl ether. In someembodiments, the treatment composition may substantially dissolve thetreatable material. While the inventive alkoxyvinyl ethers can be usedin any suitable equipment and methods, examples of such methods aredisclosed by WO2012/121749 and WO2010/094019; the disclosure of which ishereby incorporated by reference.

In another embodiment, the alkoxyvinyl ether may be used in a processfor forming a composition. The process includes providing a solute andcontacting the solute with a solvent including the alkoxyvinyl ether. Insome embodiments, the alkoxyvinyl ether may substantially dissolve thesolute. Except for water, the inventive alkoxyvinyl ethers are misciblewith conventional organic as well as fluorinated solvents.

In an embodiment, the alkoxyvinyl ether may be used in conventionalequipment and in a process for providing electrical insulation. Theprocess includes providing a first charged surface, providing a secondcharged surface, and contacting the first charged surface and the secondcharged surface with a dielectric composition including the alkoxyvinylether. In some embodiments, the dielectric composition forms acontinuous pathway between the first charged surface and the secondcharged surface. In some embodiments, the first charged surface and thesecond charged surface may be substantially submerged in the dielectriccomposition.

The following Examples are provided to illustrate certain aspects of theinvention and shall not limit the scope of the appended claims.

EXAMPLES Example 1. Reaction of CF₃CFHCFHC₂F₅ (I) with CH₃OH/KOH

A solution of 240 g (4.27 mol) of KOH in 1400 mL of methanol was placedin a 3 L round-bottomed flask equipped with reflux condenser,thermocouple, addition funnel and magnetic stir bar. The flask wasimmersed in ice cooling bath. Vertrel® XF(1,1,1,2,2,3,4,5,5,5-decafluoropentane, I, 504 g, 2 mol) was addeddropwise to the cooled solution, while maintaining the internaltemperature below 10° C. (˜3 hours). The reaction mixture was allowed towarm to ambient temperature overnight. The next morning the reactionmixture was washed in portions with a large excess of ice water in aseparatory funnel. The fluorous layers were collected, combined, andwashed with a saturated solution of sodium bicarbonate (1 L×2), driedwith MgSO₄ and filtered to yield 448 g of crude product. Crude productsfrom three consecutive runs were combined (total 1085 g) and distilledat atmospheric pressure, using a 16-inch-long distillation column.Distillation data and the composition of the fractions is shown in Table1.

TABLE 1 Distillation of Crude Reaction Mixture Weight Pot Temp Head TempComposition (wt %) Fraction (g) (° C.) (° C.) (I) (IIa)(IIb) (III) (IV)(V) 1 12 71.6-72   56-59.8 67 33 — — — 2 11  72-72.1 59.8-60.6 63 37 — —— 3 11 72.1-72.1  62-66.1 31 68 — — — 4 22 72.1-72.5 66.1-66.5 24 76 — —— 5 27 72.5-72.7 66.5-69.1 40 60 — — — 6 22 72.7-72.7 69.1-71.9 17 83 —— — 7 20 72.7-72.9 71.9-72  4.5 95.1 — — — 8 157 73.2-73.3  72-73.2 2.996.8 — — — 9 133 73.3-73.3 73.2-73.2 — 99.4 — — — 10 164 73.3-73.873.2-73.2 — 98.5 1.0 — — 11 111 73.8-74.4 73.2-73.3 — 98.7 0.8 — — 12117 74.8-75.9 73.3-73.5 — 99.4 0.6 — — 13 124 75.9-80.8 73.5-73.6 — 99.30.6 — — 14 58 81-96 73.6-75  — 95 3.7 1 — 15 17  96-116  75-76.2 — 897.8 2.7 — 16 18 116-130 76.2-80.4 — 68 17.1 14.7 — POT 44 4 5 27 47

Combined fractions 8-13 (806 g total, yield 55%) were analyzed by NMRand shown to be a ˜99% pure mixture of compounds IIa and IIb in ratio85:15

Compound IIa:

¹H NMR (CDCl₃, J, Hz): 3.98 (3H, s), 5.74 (1H, q, 8.4), ppm

¹⁹F NMR (CDCl₃, J, Hz): −55.34 (3F, d, 8.1), −83.23 (3F, t, 1.5),−119.34 (2F, s) ppm

Compound IIb:

¹H NMR (CDCl₃, δ, J, Hz): δ 3.92 (3H, s), 5.57 (1H, t, 13.3) ppm

¹⁹F NMR (CDCl₃, J, Hz): −69.42 (3F, s), −85.78 (3F, t, 2.5), −110.70(2F, dt, 13.8, 2.5) ppm

Compound III:

¹H NMR (CDCl₃, J, Hz): 3.58 (3H, s), 5.62 (1H, dd, 28.1, 15.6) ppm

¹⁹F (CDCl₃, J, Hz): −60.66 (3F, m, 9.9, 4.5), −80.36 (3F, d, 8.8),−118.90 (1F, tm, 28.1), −127.24 (1F, dd, 28.1, 15.3) ppm

Compound IV:

¹H NMR (CDCl₃, J, Hz): 2.84 (2H, m), 3.62 (3H, q, 1.2) ppm

¹⁹F (CDCl₃, J, Hz): −73.41 (3F, d, 9.9), −83.86 (3F, t, 4.5), −124.71(2F, A:B q, 286.0), −130.45 (1F, m, 9.1) ppm

Compound V:

¹H NMR (CDCl₃, J, Hz): 3.41 (6H, s), 5.48 (1H, d, 33.2) ppm

¹⁹F (CDCl₃, J, Hz): −73.24 (3F, d, 9.3), −78.23 (3F, d, 6.8), −120.87(1F, dm, J_(d)=33.2) ppm

Example 2. Reaction of CF₃CFHCFHC₂F₅ with CF₃CH₂OH/KOH

A 500 mL 3-neck round bottomed flask was equipped with an additionfunnel, thermocouple, and reflux condenser. Under a nitrogen blanket,200 mL of 45 wt % KOH/water solution was added, along with 2 g ofcatalyst—tetrabutylammonium bromide (TBAB, phase transfer catalyst).This mixture was cooled in an ice bath down to ˜5° C. and 50 g (˜36 mL,0.5 mol) of trifluoroethanol was added dropwise over 30 mins period at10° C. Addition of trifluoroethanol was followed by slow addition of 125g (0.5 mol) of I at 5-10° C. (˜30 min). The reaction mixture was slowlybrought to ambient temperature (˜4 hrs). After stirring at ambienttemperature for an additional ˜3 hrs, the reaction mixture was pouredinto 500 mL of water, fluorous layer separated, washed with water, driedover MgSO₄, filtered and distilled using a Vigreux column. 87 g (yield56%) of fraction b.p. 95-98° C. was isolated. The fraction containedisomers VIa and VIb in a ratio of 72:25, respectively and about 3% ofother isomeric products.

Compound VIa:

¹H NMR (CDCl₃, J, Hz): 4.39 (2H, q, 7.7) 5.98 (1H, q, 7.6), ppm

¹⁹F NMR (CDCl₃, J, Hz): δ−57.32 (3F, dq, 7.5, 1.7), −75.19 (3F, t, 7.8),−83.16 (3F, d, 0.7), −118.83 (2F, s) ppm

Compound VIb:

¹H NMR (CDCl₃, J, Hz): δ 5.80 (1H, t, 12.9), 4.36 (2H, q, 7.9) ppm

¹⁹F NMR (CDCl₃, J, Hz): −69.20 (3F, s), −75.1 (3F, t, 7.6), −85.54 (3F,t, 2.3), −112.23 (2, F dm, 12.9, 2.1) ppm

Example 3. Reaction of CF₃CFHCFHC₂F₅ with CH₃CH₂OH/KOH

Using the procedure described above in Example 1, 126 g (0.5 mol) of I,was added to a solution of 70 g (1.07 mol) of KOH in 400 ml of ethanol.The resulting crude product isolated after washing reaction mixture withwater, drying, filtration and distillation yielded 94.4 g (yield 73%) ofmaterial with b.p. 85-89° C., which was found to be a mixture of VIIaand VIIb in a ratio 75:25, containing 3% isomeric material (NMR andGC/MS).

Compound VIIa:

¹H NMR (CDCl₃, J, Hz): 1.36 (3H, t, 7.4), 4.19 (2H, q, 7.4), 5.74 (1H,q, 8.0) ppm

¹⁹F NMR (CDCl₃, J, Hz): −56.34 (3F, dt, 8.1, 2.2), −83.18 (3F, t, 1.9),−119.23 (2F, s) ppm

Compound VIIb:

¹H NMR (CDCl₃, J, Hz): 1.35 (3H, t, 7.3), 4.14 (2H, q, 7.3), 5.74 (1H,t, 12.8) ppm

¹⁹F NMR (CDCl₃, J, Hz): −69.58 (3F, s), −85.81 (3F, t, 2.5), −111.27(2F, dm, J_(d)=13.8) ppm

Example 4. Reaction of CF₃CFHCFHC₂F₅ with (CH₃)₂CHOH/KOH

Following the procedure described above in Example 1. Compound I (126 g,0.5 mol) was added to a solution of 70 g (1.07 mol) of KOH in 400 ml ofiso-propanol. The isolated crude product was distilled to yield 79 g(yield 61%) of a fraction with b.p. 98-99° C., containing a mixture ofVIIa and VIIb in a ratio of ˜70:30, containing 3% of other isomericmaterial (NMR, GC/MS).

Compound VIIIa:

¹H NMR (CDCl₃, J, Hz): 1.31 (6H, d, 6.0), 4.63 (1H, quint., 6.0), 5.76(1H, q, 8.0) ppm

¹⁹F NMR ((CDCl₃, J, Hz): −57.54 (3F, dt, 8.0, 2.1), −83.00 (3F, t, 1.9),−117.99 (2F, s) ppm

Compound VIIIb:

¹H NMR (CDCl₃, J, Hz): 1.31 (6H, d, 6.0), 4.56 (1H, quint., 6.0), 5.56(1H, t, 13.0) ppm

¹⁹F NMR (CDCl₃, J, Hz): −68.38 (3F, s), −85.57 (3F, t, 2.5), −111.55(2F, dq, 13.0, 2.2) ppm

Example 5. Reaction of C₃F₇CH═CFC₂F₅/C₃F₇CF═CHC₂F₅ with MeOH/KOH

Following the procedure described above in Example 1. The olefin(mixture of C₃F₇CH═CFC₂F₅ and C₃F₇CF═CHC₂F₅ in ratio ˜ 1:1) was added toa solution of KOH (20 g, 0.36 mol) in 300 ml of MeOH. After work up 105g of crude product was isolated and distilled to yield 61.5 g (yield46%), of a fraction with b.p. 107-110° C., containing a mixture of IXa,IXb, and isomeric material in ratio 45:40:15 (GC/MS, NMR)

Major isomer (content—45% in a mixture):

¹H NMR (CDCl₃, J, Hz): 3.96 (3H, t, 1.2), 5.66 (1H, t, 14.5) ppm

¹⁹F NMR (CDCl₃, J, Hz): −81.14 (3F, t, 9.5), −85.02 (3F, t, 1.9),−109.06 (2F, dm, J_(d)=14.5), −116.39 (2F, q, 9.5), −127.05 (2F, s) ppm

Minor isomer (content—40% in a mixture):

¹H NMR (CDCl₃, J, Hz): 3.92 (3H, t, 1.2), 5.73 (1H, t, 14.0) ppm

¹⁹F NMR (CDCl₃, J, Hz): δ−80.78 (3F, t, 9.2), −83.55 (3F, m), −107.16(2F, quint., 11.0), −118.55 (2F, s), −128.09 (2F, s) ppm

While the invention has been described with reference to a preferredembodiment, it will be understood by those skilled in the art thatvarious changes may be made and equivalents may be substituted forelements thereof without departing from the scope of the invention. Inaddition, many modifications may be made to adapt a particular situationor material to the teachings of the invention without departing from theessential scope thereof. Therefore, it is intended that the inventionnot be limited to the particular embodiment disclosed as the best modecontemplated for carrying out this invention, but that the inventionwill include all embodiments falling within the scope of the appendedclaims.

What is claimed is:
 1. An alkoxyvinyl ether having the followingchemical structure:R_(f)C(OR)═CHR_(f)′ wherein: R_(f) is CF₃; R_(f)′ is C₂F₅; and R is CH₃.2. The alkoxyvinyl ether of claim 1, wherein the alkoxyvinyl ether is anE-isomer.
 3. The alkoxyvinyl ether of claim 1, wherein the alkoxyvinylether is a Z-isomer.
 4. The alkoxyvinyl ether of claim 1, wherein thealkoxyvinyl ether is a mixture of E- and Z-isomers.
 5. A method forpreparing an alkoxyvinyl ether, comprising:R_(f)CFHCFHR_(f)′+Base/ROH→R_(f)C(OR)═CHR_(f)′ wherein: R_(f) is aperfluoro functional group; R_(f)′ is a perfluoro functional group; andR is an alkyl functional group.
 6. A method for preparing an alkoxyvinylether, comprising:R_(f)CF═CHR_(f)′+Base/ROH→R_(f)C(OR)═CHR_(f)′ wherein: R_(f) is aperfluoro functional group; R_(f)′ is a perfluoro functional group; andR is an alkyl functional group.
 7. An alkoxyvinyl compositioncomprising: the alkoxyvinyl ether of claim 1; a solvent including atleast one of alcohols, ethers, tetrahydrofuran (THF), amides, oraromatic solvents; and a base including at least one of KOH, NaOH, LiOH,Ca(OH)₂ tertiary amines, or alkoxides of alkali metals.
 8. A process fortransferring heat, comprising: providing an article; contacting thearticle with a heat transfer media; wherein the heat transfer mediacomprises the alkoxyvinyl ether of claim
 1. 9. The process of claim 8,wherein the boiling point of the alkoxyvinyl ether is between 72 degreesCelsius and 81 degrees Celsius.
 10. A process for treating a surface,comprising: providing a surface; contacting the surface with a treatmentcomposition; wherein the surface includes a treatable material depositedthereon; and wherein the treatment composition comprises the alkoxyvinylether of claim
 1. 11. The process of claim 10, wherein the treatmentcomposition substantially dissolves the treatable material.
 12. Aprocess for forming a composition comprising: providing a solute;contacting the solute with a solvent; wherein the solvent comprises thealkoxyvinyl ether of claim
 1. 13. A process for providing electricalinsulation, comprising: providing a first charged surface; providing asecond charged surface; contacting the first charged surface and thesecond charged surface with a dielectric composition; wherein thedielectric composition comprises the alkoxyvinyl ether of claim
 1. 14.The process of claim 13, wherein the dielectric composition forms acontinuous pathway between the first charged surface and the secondcharged surface.